Siloxane aluminum compounds



United States Patent ce 3,002,986 SILOXANE AL COMPOUNDS James F. Hyde, Midland, Mich., assignor to Dow Corning Corporation, Midland, Mich., a corporation of Michigan N0 Drawing. Filed Oct. 23, 1959, Ser. No. 848,228 2 Claims. (Cl. 260448) This invention relates to polymeric materials having both silicon and aluminum atoms in the polymer chains.

It is the object of this invention to provide novel compositions of matter which are useful as water repellents and as emulsifying agents for water-in-oil emulsions. This invention relates to compositions of the unit formula (YX) in which Y has a cyclic structure of the empirical formula -O[R SiO Al] O-, X is of the formula R2 R2 -s10s1- and z is an integer of at least 1, in which composition esesntially all of the valences of the silicon atoms not satisfied by R groups are satisfied by oxygen atoms and essentially all of the valences of the aluminum atoms are satisfied by oxygen atoms and in which composition each R is a monovalent hydrocarbon radical.

The term essentially all means that there can be attached to some of the Si atoms OH groups, OM groups or alkoxy groups which are due to incidental hydrolysis or incomplete reaction. It also means that the Al atoms can be attached to some OH or Cl groups due to incomplete reaction or incidental hydrolysis.

The cyclic Y group can be of two structural configurations OA1O-Al0- R2S i O S i Ra hereinafter designated -0Al0-Al0 and as 0 o --o.#.( iuo s hereinafter designated Thus it can be seen that the compositions (YX) can be linear in structure such as R: R2 [-0 Al-O-Al 0 Bio Si-l It is also clear that the compositions of this invention can be polycyclic in structure. bicyclic compound of the structural formula The simplest cyclic is a 3,002,986 iatented oo. 3, 11 961 These compounds each contain one (YX) unit. The cyclic compounds can also contain multiples of the (YX) 3 R2 MOSiOSiOM where M is an alkali metal and R is as above defined. This reaction is best carried out in a mutual solvent such as ethers such as diethylether, dibutylether or amines such as pyridine. If desired, mixed solvents such as mixtures of hydrocarbons with ethers or halogenated hydrocarbons with ethers can'be employed. It is desirable that the reaction be carried out under anhydrous conditions since water tends to hydrolyze both the aluminum bonded chlorine and the SiOAl bonds.

The reaction of this invention can produce any of the complex structures shown above and generally in any one reaction a mixture of compounds having the above structures is obtained. The progress of the reaction is indicated by the precipitation of MCI which is a byproduct of the reaction. The lower molecular weight products of this invention are soluble in the reaction solvents and can be recovered therefrom by evaporation of the solvent.

The starting materials (1) of this invention can be prepared by reacting aluminum chloride with completely condensed diorganosiloxanes in accordance with the.v

method shown in U.S. Patent 2,645,654. Briefly the.

siloxane and aluminum chloride are heated at tempera tures of to C. under anhydrous conditions... This results in the formation of chlorosiloxanes and the cyclic compounds 1), In general, the reaction produces a mixture of cyclics of the structure ClAl-O-AlOl and OlAl A101 The alkali metal salts (2) employed in this. invention are best prepared by reacting ethoxysilanes of the formula R Si(OC H with alkali metal alkoxides under substantially anhydrous conditions as shown in U.S. Patent 2,567,110.

For the purpose of this invention R can be any monovalent hydrocarbon radical such as aliphatic hydrocarbon radicals such as methyl, ethyl, butyl, t-butyl, octadecyl, myricyl, vinyl, allyl, hexenyl, octadecenyl, butaa Example I 1 and were dissolved in 0c. of dry benzene. 31.5 g. of NaO[(CH SiO] Na were added as a dry powder. 30 cc. of 'dry ether were: then added and the reaction mixture was stirred for 2 days. It was then filtered to remove the precipitated. sodium chloride together with a complex polymeric. material. The solvent was then evaporated whereupon there was obtained a light strawcolored friable material which was a mixture of compounds ofthe formulae and l I Al 1 Theinsoluble polymeric material which was precipitated during reaction was a mixture of materials having cyclic andlinear configurations such as those set forth.

in column 11 Example 2" When the following siloxane-aluminum compounds' arei reacted with the following alkali metal silanol salts the following products are obtained.

That which is claimed is:

1. A composition of matter of the unit formula (YX) in which Y has a cyclic structure and is of the formula -0[R SiO Al] O-, X is of the formula R, R, Si0Si and z is an integer from 1 to 20 inclusive in which composition R is a monovalent hydrocarbon radical of from 1 to 30 inclusive carbon atoms, any valences of the silicon atoms not satisfied by R groups and oxygen atoms 10 being satisfied by radicals selected from the group consisting of hydroxyl, alkoxy and OM where M is an alkali metal and in which composition any valences of the aluminum atoms not satisfied by oxygen atoms being satisfied by substituents selected from the group consisting of hydroxyl groups and chlorine atoms.

2. A composition in accordance with claim 1 in which each R is methyl.

No references cited. 

1. A COMPOSITION OF MATTER OF THE UNIT FORMULA (YX)Z IN WHICH Y HAS A CYCLIC STRUCTURE AND IS OF THE FORMULA -O(R2SIO2AL)2O-, X IS OF THE FORMULA 